EP1916282A1 - Wasserbasislack und lackiertes stahlblech - Google Patents
Wasserbasislack und lackiertes stahlblech Download PDFInfo
- Publication number
- EP1916282A1 EP1916282A1 EP05768446A EP05768446A EP1916282A1 EP 1916282 A1 EP1916282 A1 EP 1916282A1 EP 05768446 A EP05768446 A EP 05768446A EP 05768446 A EP05768446 A EP 05768446A EP 1916282 A1 EP1916282 A1 EP 1916282A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- water
- group
- coating composition
- acid
- calcium carbonate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000008199 coating composition Substances 0.000 title claims abstract description 50
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 9
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- 239000011248 coating agent Substances 0.000 claims abstract description 75
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 71
- 229920005989 resin Polymers 0.000 claims abstract description 34
- 239000011347 resin Substances 0.000 claims abstract description 34
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 33
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 32
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- 239000006185 dispersion Substances 0.000 claims abstract description 21
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- 150000003839 salts Chemical class 0.000 claims abstract description 15
- 239000007787 solid Substances 0.000 claims abstract description 15
- 239000000049 pigment Substances 0.000 claims abstract description 14
- 229940088417 precipitated calcium carbonate Drugs 0.000 claims abstract description 5
- 239000003822 epoxy resin Substances 0.000 claims description 49
- 229920000647 polyepoxide Polymers 0.000 claims description 49
- 150000001875 compounds Chemical class 0.000 claims description 23
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
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- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000005711 Benzoic acid Substances 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
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- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
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- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 4
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- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
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- 238000010438 heat treatment Methods 0.000 description 3
- 238000010348 incorporation Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 3
- KDVYCTOWXSLNNI-UHFFFAOYSA-N 4-t-Butylbenzoic acid Chemical compound CC(C)(C)C1=CC=C(C(O)=O)C=C1 KDVYCTOWXSLNNI-UHFFFAOYSA-N 0.000 description 2
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 2
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
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- 239000005062 Polybutadiene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
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- 125000002723 alicyclic group Chemical group 0.000 description 2
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- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
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- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
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- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- NKHAVTQWNUWKEO-NSCUHMNNSA-N monomethyl fumarate Chemical compound COC(=O)\C=C\C(O)=O NKHAVTQWNUWKEO-NSCUHMNNSA-N 0.000 description 1
- 229940005650 monomethyl fumarate Drugs 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000008165 rice bran oil Substances 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 239000003813 safflower oil Substances 0.000 description 1
- 235000005713 safflower oil Nutrition 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 150000008054 sulfonate salts Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000003142 tertiary amide group Chemical group 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 150000003566 thiocarboxylic acids Chemical class 0.000 description 1
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 238000006886 vinylation reaction Methods 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical class O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/10—Block or graft copolymers containing polysiloxane sequences
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
- C09D5/084—Inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/67—Particle size smaller than 100 nm
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/68—Particle size between 100-1000 nm
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/14—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
Definitions
- the present invention relates to a water-base coating composition and a coated steel sheet.
- Solvent type coatings have mainly been used for anticorrosion coating in large structures, such as ships, bridge, tanks and plants.
- the demand for water-base coatings using water as a solvent has recently been increasing due to consideration of environmental preservation, such as reduction in volatile organic compounds (VOC) and consideration of the safety during coating or storage of coatings.
- VOC volatile organic compounds
- Patent document 1 discloses an aqueous dispersion of a vinyl-modified epoxy ester resin having a specific structure. It also discloses that a coating film formed with a water-base coating composition containing the aqueous dispersion has excellent corrosion resistance. However, even if coating is carried out using such coating compositions, the problems mentioned above cannot be solved completely.
- Patent document 2 discloses a specific block polymer containing a polyorganosiloxane unit and a polyalkylene oxide unit. It is disclosed that when a small amount of the block polymer is added to a coating material, it can impart surface modification effects, such as a surface tension regulating function and an adhesiveness imparting function, to the coating material. However, use of this compound for an anticorrosive, ambient temperature curing type coating is not disclosed.
- Patent document 3 discloses calcium carbonate suitable for incorporation into water-based coating compositions. However, use of this coating for water-base coatings that are required to have high anticorrosion property is not disclosed.
- an object of the present invention is to provide a water-base coating composition and a coated steel sheet coated with the water-base coating composition, the composition being suitable for use in ships, bridges, etc. and having excellent gloss, coating film appearance and anticorrosion property, which properties do not deteriorate even in coating under high humidity conditions.
- the present invention is a water-base coating composition including an aqueous dispersion type vinyl-modified epoxy ester resin and calcium carbonate, wherein the calcium carbonate is precipitated calcium carbonate treated with a salt of a vinyl polymer having a carboxyl group and is contained in the coating composition in a proportion of from 20 to 50% by volume in a solid content, and a volume ratio of pigment/total solid content of the coating is 50% or less.
- the calcium carbonate has an average particle diameter of from 0.01 to 0.5 ⁇ m.
- the salt of a polymer having a carboxyl group be a sodium, ammonium and/or amino salt of a vinyl polymer obtained by polymerizing a vinyl monomer composition containing at least one ⁇ , ⁇ unsaturated dicarboxylic acid selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, maleic acid and itaconic acid.
- the aqueous dispersion type vinyl-modified epoxy ester resin is desirably one obtained by subjecting a condensate (c) produced by condensing an epoxy resin (a) and a fatty acid (b) as essential components and a vinyl monomer composition (d) containing an acid group-containing monomer to graft polymerization.
- the amount of the mixture (d) of the vinyl compounds is not less than 15 parts by mass based on 100 parts by mass of the combined weight of the condensate (c) and the mixture (d).
- the water-base coating composition further contains a silicone-modified epoxy resin.
- the silicone-modified epoxy resin includes a compound represented by the following general formula (1): wherein U 1 is -O(R 3 O) b -, where R 3 is -(CH 2 ) c - or -CH 2 CH(CH 3 )-, and U 2 is a structure represented by or U 1 is a structure represented by and U 2 is -O(R 3 O) b -, where R 3 is -(CH 2 ) c - or -CH 2 CH(CH 3 )-, wherein R 1 and R 2 are each an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 9 carbon atoms, R 4 is hydrogen or a methyl group, a is an integer of from 1 to 135, b is an integer of from 2 to 230 and c is an integer of from 1 to 4, A is an organic group bonding to its adjoining -CHR 4 - with a carbonyl group inter
- the present invention is also directed to a coated steel sheet having a coating film formed from the water-base coating composition mentioned above.
- the water-base coating composition of the present invention contains a specific water-dispersible resin and also contains a relatively large amount of calcium carbonate having been subjected to a specific treatment. That is, incorporation of calcium carbonate relatively more than usual can increase the thickness of a coating film in coating. If it is possible to thicken a coating film, the anti-corrosiveness will thereby be enhanced. As a result of this, it is possible to improve the anti-corrosiveness. Further, choosing a specific species as the calcium carbonate for use prevents occurrence of problems such as deterioration in appearance. Therefore, a coating composition is obtained which solves all the problems, namely, to provide a water-base, ambient temperature drying coating, to improve anti-corrosiveness, and to maintain appearance and the like. In addition, the water-base coating composition of the present invention has an excellent property in that deterioration in appearance of a coating film does not occur even if coating is performed under high humidity conditions.
- the water-base coating composition of the present invention contains calcium carbonate in a proportion of from 20 to 50% by volume in a solid content. This can increase the viscosity of the coating and therefore it is possible to increase the thickness of a coating film formed by one coating operation. As a result, it is possible to improve the anticorrosion property of a coating film.
- the amount of the calcium carbonate to be incorporated is preferably from 20 to 50% by volume, and more preferably from 30 to 50% by volume. If it is less than 20% by volume, the above-mentioned effects can not be obtained sufficiently. If it is more than 50% by volume, coating film appearance, such as gloss, will be affected.
- the calcium carbonate is precipitated calcium carbonate treated with a salt of a vinyl polymer having a carboxyl group.
- the precipitated calcium carbonate thus treated exerts good dispersibility in water and therefore it will not cause problems such as deterioration in appearance even when it is incorporated in an amount as large as from 20 to 50% by volume in a solid content.
- the water-base coating composition of the present invention may be one which further contains a pigment other than the above-mentioned calcium carbonate. In such a case, it must be contained in a proportion such that the volume ratio of a pigment/a total solid content of the coating may be 50% by volume or less. By adjusting the amount to within the above-mentioned range, it is possible to maintain the gloss of a coating film and it therefore is possible to form a coating film with good appearance.
- Examples of other pigment which can be used for the water-base coating composition of the present invention include extenders such as precipitated barium sulfate, clay and talc; coloring pigments such as titanium oxide and carbon; and rust preventive pigments such as zinc phosphate.
- the salt of a vinyl polymer having a carboxyl group is desirably a sodium, ammonium and/or amino salt of a vinyl polymer obtained by polymerizing a vinyl monomer composition containing at least one ⁇ , ⁇ -unsaturated dicarboxylic acid selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, maleic acid and itaconic acid.
- the salt of a vinyl polymer having a carboxyl group is desirably a copolymer of an ⁇ , ⁇ -unsaturated monocarboxylic acid (acrylic acid, methacrylic acid, crotonic acid, etc.) and an ⁇ , ⁇ -unsaturated dicarboxylic acid (maleic acid, itaconic acid, and the like). It is more desirable that the amount of the ⁇ , ⁇ -unsaturated dicarboxylic acid is 120 parts by mass or less based on 100 parts by mass of the ⁇ , ⁇ -unsaturated monocarboxylic acid.
- the salt of a vinyl polymer having a carboxyl group desirably has a number average molecular weight of from 500 to 50000. By adjusting to within such a range, it is possible to achieve a favorable treatment on calcium carbonate.
- the number average molecular weight is a value obtained, in terms of polystyrene, through measurement by gel permeation chromatography (GPC).
- the salt of a vinyl polymer having a carboxyl group can be obtained by performing polymerization of the monomer in a solvent such as water and organic solvents, and neutralizing the resulting vinyl polymer with a sodium compound, an ammonium compound, an organic amine compound, or the like.
- the treatment of the calcium carbonate with the salt of a vinyl polymer having a carboxyl group may be a treatment by wet grinding, drying/powderization, or the like. In the treatment, it is desirable to cause from 0.01 to 10 parts by mass, based on 100 parts by mass of the calcium carbonate solid content, of the salt of a vinyl polymer having a carboxyl group to be adsorbed.
- the average particle diameter of the calcium carbonate is desirably from 0.01 to 0.5 ⁇ m. If it is less than 0.01 ⁇ m, a problem that the calcium carbonate easily flocculates and the storage stability of a coating will deteriorate may arise. If it exceeds 0.5 ⁇ m, a problem that good gloss of a coating film can not be obtained may arise.
- the average particle diameter as referred to herein is the length of a side of a cubic crystal determined from the specific surface area measured by the gas absorption method (BET method), while assuming calcium carbonate particles to be cubic particles.
- a commercially available product may also be used as the calcium carbonate treated with the salt of a vinyl polymer having a carboxyl group.
- LUMINUS manufactured by Maruo Calcium Co., Ltd.
- the water-base coating composition of the present invention contains the aqueous dispersion type vinyl-modified epoxy ester resin.
- the aqueous dispersion type vinyl-modified epoxy ester resin is a resin obtained by modifying an epoxy ester resin with a compound containing a vinyl group and is a water-dispersible, ambient temperature curing resin. It has a characteristic of being excellent particularly in anticorrosion property.
- the aqueous dispersion type vinyl-modified epoxy ester resin is desirably one obtained by subjecting a condensate (c) produced by condensing an epoxy resin (a) and a fatty acid (b) as essential components and the vinyl monomer composition (d) containing an acid group-containing monomer to graft polymerization.
- the aqueous dispersion type vinyl-modified epoxy ester resin obtained by the method shown above has a particularly excellent characteristic with respect to anticorrosion property.
- the proportions of the epoxy resin (a) and the fatty acid (b) used in the synthesis of the condensate (c) it is desirable to use them so that the equivalent ratio of the epoxy groups in the epoxy resin may be in excess of that of the carboxyl groups originating in a fatty acid.
- epoxy resin (a) examples include various epoxy resins such as bisphenol type epoxy resins, alicyclic epoxy resins, phenol novolak type epoxy resins, polyethylene glycol-based epoxy resins, and epoxidized polybutadiene.
- EPICLON 850, 1050, 3050, 4050, 7050 epoxy resins manufactured by Dainippon Ink & Chemicals, Inc.
- EPICOAT 828, 834, 1001, 1004, 1007, 1009 epoxy resins manufactured by Shell, Netherlands
- DER 660,661J, 662,664J, 667J, 668,669J epoxy resins manufactured by the Dow Chemical Co., Ltd. USA
- UNOX 201, 289 epoxy resins manufactured by Union Carbide Corporation, U.S.A.
- UNOX 201, 289 epoxy resins manufactured by Union Carbide Corporation, U.S.A.
- EPICLON N-740, 775 (Dainippon Ink & Chemicals, Inc.) may be used, for example.
- EPICOAT 812 epoxy resin manufactured by Shell, Netherlands
- EPOLIGHT 40E, 200E, 400E epoxy resins manufactured by Kyoeisha Chemical Co., Ltd.
- BF-1000 an epoxy resin manufactured by Adeka Argus Industry Co., Ltd.
- Adeka Argus Industry Co., Ltd. an epoxy resin manufactured by Adeka Argus Industry Co., Ltd.
- the epoxy resin (a) may be used singly or as a mixture of two or more kinds thereof. It is more desirable to use a bisphenol type epoxy resin because of its excellent corrosion resistance as a major ingredient.
- the fatty acid (b) is not particularly restricted and examples thereof include drying oil fatty acids such as tung oil fatty acid, linseed oil fatty acid, dehydrated caster oil fatty acid, castor oil fatty acid, tall oil fatty acid, cottonseed oil fatty acid, soybean oil fatty acid, olive oil fatty acid, safflower oil fatty acid and rice bran oil fatty acid, or nondrying oil fatty acids such as hydrogenated coconut oil fatty acid, coconut oil fatty acid and palm oil fatty acid.
- drying oil fatty acids such as tung oil fatty acid, linseed oil fatty acid, dehydrated caster oil fatty acid, castor oil fatty acid, tall oil fatty acid, cottonseed oil fatty acid, soybean oil fatty acid, olive oil fatty acid, safflower oil fatty acid and rice bran oil fatty acid, or nondrying oil fatty acids such as hydrogenated coconut oil fatty acid, coconut oil fatty acid and palm oil fatty acid.
- fatty acids such as oleic acid, linoleic oil, linolenic acid, eleostearic acid, ricinoleic acid, and saturated fatty acids such as octylic acid, lauric acid and stearic acid purified from those oil fatty acid.
- the fatty acid may be used singly or as a mixture of two or more kinds thereof.
- An unreacted epoxy group originating in the epoxy resin (a) may be capped with an acid group-containing compound.
- Examples of the acid group-containing compound include organic carboxylic acids such as benzoic acid, p-tert-benzoic acid, isooctanoic acid, isodecanoic acid, cyclohexanoic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, himic acid (a product of Hitachi Chemical Co., Ltd.), maleic acid, fumaric acid, adipic acid, sebacic acid, dimer acid, trimellitic acid and pyromellitic acid.
- organic carboxylic acids such as benzoic acid, p-tert-benzoic acid, isooctanoic acid, isodecanoic acid, cyclohexanoic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, himic acid (a product of Hitachi Chemical Co., Ltd.), maleic acid, fumaric acid, adipic acid, se
- Examples of such a monobasic acid compound (e) include conventional organic carboxylic acids such as benzoic acid, p-tert-benzoic acid, isooctanoic acid, isodecanoic acid and cyclohexanoic acid.
- the epoxy ester and the mixture (d) of the vinyl compounds containing an acid group-containing monomer are subjected to polymerization reaction in the presence of a radical polymerization initiator under heating conditions, in an organic solvent if necessary, to obtain a graft polymerization product of the epoxyester and the vinyl compound (vinyl-modified epoxy ester resin).
- the reaction may be performed under a gauge pressure within the range of from 1 to 100 kg/cm 2 , and at a reaction temperature within the range of from 50 to 150°C. In some cases, polymerization may be performed under a pressure more than the above and at a temperature lower than the above.
- the amount of nonvolatile matter in polymerization is desirably within the range of from 1 to 90% by mass, and more desirably within the range of from 40 to 80% by mass.
- the mixture (d) of the vinyl compounds containing an acid group-containing monomer is desirably a mixture containing an aromatic vinyl compound, an alkyl (meth)acrylate having an alkyl group having 4 or more carbon atoms, and an acid group-containing vinyl compound.
- the amount of the mixture (d) of the vinyl compounds containing an acid group-containing monomer is 15 parts by mass or more based on 100 parts by mass of the combined amount of the condensate (c) containing the epoxy resin (a) and the fatty acid (b) and the mixture (d) of the vinyl compounds containing an acid group-containing monomer.
- the amount of the mixture (d) of the vinyl compounds containing an acid group-containing monomer is 15% or less, a product failing to have a desired balance between corrosion resistance and hardness will be obtained.
- the vinyl-modified epoxy ester resin has an acid group derived from the acid group-containing monomer, and this acid group is essential for make it water-base in a step which will be performed later.
- the concentration of the acid group is desirably within the range of from 15 to 50 gmKOH/g in terms of the acid value of the solid content in the vinyl-modified epoxy ester resin. When it is within this range, it is possible to achieve dispersion in water well and also achieve good adhesiveness to a substrate or pigment dispersing property. It is also possible to obtain excellent performances caused by water of a resulting coating film, namely, corrosion resistance, water resistance, alkali resistance, and the like.
- the number average molecular weight of the vinyl-modified epoxy ester resin be within the range of from 1,000 to 100,000.
- a product having a number average molecular weight within the above range is excellent in corrosion resistance, water resistance, etc., and can also be dispersed well in water.
- the acid group-containing monomer include monomers having a carboxyl group (A), such as monocarboxylic acids having an unsaturated double bond, e.g.
- (meth)acrylic acid 2-carboxyethyl acrylate, crotonic acid, vinylacetic acid, monovinyl adipate, monovinyl sebacate, monomethyl itaconate, monomethyl maleate, monomethyl fumarate, mono[2-(meth)acryloyloxyethyl] succinate, mono[2-(meth)acryloyloxyethyl] phthalate, mono[2-(meth)acryloyloxyethyl] hexahydrophthalate and sorbic acid; and unsaturated dicarboxylic acids, e.g. itaconic acid, maleic acid and fumaric acid.
- unsaturated dicarboxylic acids e.g. itaconic acid, maleic acid and fumaric acid.
- cycloalkyl (meth)acrylates alkyl-substituted cycloalkyl (meth)acrylates; (meth)acrylates having an alkyl or aralkyl group (B); and aromatic vinyl compounds (C).
- (A) which is an essential ingredient, an alkyl (meth)acrylate having an alkyl group having 4 or more carbon atoms, a cycloalkyl group or an alkyl-substituted cycloalkyl group, and more preferably an alkyl (meth)acrylate having an alkyl group having 4 or more carbon atoms among the monomers (B) shown above.
- monomers (A), (B) and (C) is preferred.
- monomers shown below can also be used as the mixture (d) of vinyl compounds containing an acid group-containing monomer: ⁇ -alkoxyalkyl (meth)acrylates (D); vinyl esters of carboxylic acids (E); crotonic acid esters (F); unsaturated dibasic acid diesters (G); cyano group-containing vinyl monomers (H); fluoroolefins (I); chlorinated olefins (J); ⁇ -olefins (K); alkyl vinyl ethers (L); cycloalkyl vinyl ethers (M); tertiary amide group-containing vinyl monomers (N); (meth)acrylic acid esters containing a hydroxyl group (O); allyl compounds containing a hydroxyl group (P); vinyl ether compounds containing a hydroxyl group (Q); unsaturated carboxylic acid amide compounds containing a hydroxyl group (R); unsaturated fatty acids containing a hydroxy
- the amount of the mixture (d) of the vinyl compounds containing acid group-containing monomers used is desirably 15 parts by mass or more based on 100 parts by mass of the combined amount of the condensate (c) containing the epoxy resin (a), the fatty acid (b) and, if necessary, the monobasic acid compound (e) and the mixture (d) of the vinyl compounds containing acid group-containing monomers.
- This raw material proportions are determined in consideration of the balance of the corrosion resistance and the hardness of a coating film to be obtained.
- the amount of the mixture (d) of the vinyl compounds containing acid group-containing monomers less than 15 parts by will result in a coating film lacking a desired balance between corrosion resistance and hardness.
- radical polymerization initiator used for the reaction of the mixture (d) of the vinyl compounds containing acid group-containing monomers is not particularly restricted, if it is one generally used. Such radical polymerization initiator may be used singly or in combination of two or more.
- the amount of the radical polymerization initiator used is preferably within the range of from 0.1 to 10 parts by mass based on 100 parts of all the monomers (mixture (d) of the vinyl compounds containing acid group-containing monomers).
- the amount of the radical polymerization initiator, the reaction temperature and a chain transfer agent may be used.
- the chain transfer agent include alkylmercaptans such as n-octylmercaptan, n-dodecylmercaptan and tert-dodecylmercaptan; aromatic mercaptans such as benzylmercaptan and dodecylbenzylmercaptan; and thiocarboxylic acids such as thiomalic acid, their salts, alkyl esters, or polythiols.
- the amount of the chain transfer agent may depend on the amount of the radical polymerization initiator used and the reaction temperature. In obtaining a polymer having a relatively low molecular weight, a chain transfer agent may be used in an amount of from 0.2 to 30% by mass based on the weight of all monomers.
- graft polymerization may be performed with use of an organic solvent.
- Use of an organic solvent can reduce the viscosity of the reactant and therefore makes it possible to efficiently obtain a uniform product.
- the organic solvent for use for this purpose is not particularly restricted and any organic solvent may be used if it is an organic solvent conventionally used.
- the resulting vinyl-modified epoxy ester resin may be made water-base by neutralizing part or all of the acid groups in the resin with a neutralizer, and subsequently adding water. In such a way, an aqueous dispersion of the vinyl-modified epoxy ester resin can be prepared.
- the aqueous dispersion type vinyl-modified epoxy ester resin can be formed by neutralizing part or all of the acid groups in the resulting vinyl-modified epoxy ester resin with a basic compound, and dissolving or dispersing the neutralized polymer in water.
- an emulsifier and/or a dispersion stabilizer may be used together.
- the emulsifier various types of emulsifiers, such as ionic emulsifiers, e.g. anionic emulsifiers and cationic emulsifiers, and nonionic emulsifiers may be used.
- the anionic emulsifiers are not particularly restricted and examples thereof include alkyl(benzene) sulfonate salts, alkyl sulfates, polyoxyethylene alkylphenol sulfate salts, styrene sulfonate salts, vinyl sulfate salts, or their derivatives.
- the cationic emulsifiers are not particularly restricted and examples thereof include lauryltrimethylammonium chloride, didecyldimethylamnmonium chloride and lauryldimethylbenzylammonium chloride.
- the nonionic emulsifiers are not particularly restricted and examples thereof include polyoxyethylene alkylphenol ethers, polyoxyethylene alkyl ethers, polyoxyethylene higher fatty acid esters, ethylene oxide-propylene oxide block copolymers, or their derivatives. These may be used singly or in combination of two or more thereof.
- the amount of the emulsifier used is desirably within a range up to 10 parts by mass based on 100 parts by mass of the total resin solid content, and more desirably within the range of from 0.1 to 5 parts by mass.
- the water-base coating composition of the present invention further contains the above-mentioned silicone-modified epoxy resin.
- inclusion of the silicone-modified epoxy resin is preferred also because the adhesiveness of a coating film is improved more.
- the silicone-modified epoxy resin preferably is a compound represented by general formula (1) and/or a compound represented by the general formula (2).
- the organic group contained in A in general formulas (1) and (2) has, for example, at least one chemical structural moiety selected from the group consisting of nonreactive hydrocarbon groups, a hydroxyl group, acid groups, an amino group, an ammonium group, a cyano group, a halogen atom, an amide bond, a cyclic ether group, an alkylene oxide unit, an alkoxy silyl group, an ultraviolet-absorbing group and a tetramethyl-4-piperidyl group.
- the acrylic compound in an amount of from 1.8 to 2.2 molar times as much as the diamine compound and to use the diepoxy compound in an amount of from X+0.8 to X+1.2 moles for X moles of the product.
- the silicone-modified epoxy resin can be obtained also by the steps of subjecting a diamine compound having one unit selected from the group consisting of a polyalkylene oxide unit and a polyorganosiloxane unit and having a primary amino group at each of both terminals to a Michael addition reaction to an acrylic compound represented by general formula (3), thereby providing a product; further reacting the product with a diepoxy compound having a unit other than the unit which the diamine compound has and having an epoxy group at each of both terminals, thereby obtaining a silicone-modified epoxy resin having epoxy groups at both terminals; and reacting a secondary amine compound to the epoxy groups at both terminals of the resulting silicone-modified epoxy resin.
- silicone-modified epoxy resin by the steps of subjecting a diamine compound represented by the following general formula (4) to a Michael addition reaction to an acrylic compound represented by general formula (3), thereby obtaining a product; and further reacting the product with a diepoxy compound represented by the following general formula (5): wherein R 1 and R 2 are each an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 9 carbon atoms, a is an integer of from 1 to 135. wherein R 3 is -(CH 2 ) c - or -CH 2 CH(CH 3 )-, and b is an integer of from 2 to 230.
- the method for the preparation of the silicone-modified epoxy resin includes the steps of subjecting a diamine compound represented by the following general formula (6) to a Michael addition reaction to an acrylic compound represented by general formula (3), thereby obtaining a product; and further reacting the product with a diepoxy compound represented by the following general formula (7): H 2 N-C 3 H 6 O(R 3 O) b C 3 H 6 -NH 2 (6) wherein R 3 is -(CH 2 ) c - or -CH 2 CH(CH 3 )-, and b is an integer of from 2 to 230.
- R 1 and R 2 are each an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 9 carbon atoms, and a is an integer of from 1 to 135.
- the silicone-modified epoxy resin can be obtained also by the steps of subjecting a diamine compound represented by the above general formula (4) or (6) to a Michael addition reaction to an acrylic compound represented by the above general formula (3), thereby obtaining a product; further reacting the product with a diepoxy compound represented by the above general formula (5) or (7), thereby obtaining a silicone-modified epoxy resin having epoxy groups on its both terminals; and reacting a secondary amine compound to the epoxy groups at both the terminals of the resulting silicone-modified epoxy resin.
- the water-base coating composition of the present invention can be used, if necessary, after incorporation of additives suitable for various applications, for example, various known and conventional additives such as metal driers, antioxidants, defoaming agents and thickeners.
- the water-base coating composition of the present invention may also be used together with various water-base resins.
- Such resins are desirably resins having active hydrogen-containing groups.
- the form, kind and the like thereof are not restricted.
- the method for the production of the water-base coating composition is not particularly restricted and it can be prepared, for example, by dispersing the aforementioned calcium carbonate filler and other pigments with a resin or additive for pigment dispersion or, in some cases, the water-based vinyl-modified epoxy ester resin, thereby preparing a mill base of a pigment, and then adding the water-based vinyl-modified epoxy ester resin, various additives and water or solvent for adjusting the viscosity, followed by well mixing.
- the water-base coating composition of the present invention can be coated by airless coating or a conventional method using a brush, a trowel, a roller or the like.
- airless coating is preferred.
- the film thickness in coating it is desirable that a dry coating film has a thickness of from 50 to 200 ⁇ m. If the dry film thickness exceeds 250 ⁇ m, problems with respect to sagging property or the like will arise.
- the water-base coating composition of the present invention be used for coating on metal materials, such as iron-based substrates, zinc-based substrates and aluminum-based substrates. It is particularly suitable for coating large structures made of the above-mentioned base materials. Furthermore, it can be used suitably for ship cabin coating, in which deterioration of gloss due to increase in humidity may become a serious problem since coating in a hermetically sealed space is needed.
- the present invention also encompasses the aforementioned coated steel sheet having a coating film formed from the water-base coating composition mentioned above.
- the water-base coating composition of the present invention is an ambient drying water-base coating composition having excellent properties such as gloss, coating film appearance, anticorrosion property and moisture resistance. Because of being excellent in such physical properties, coating compositions for coating ships, bridges and the like, which have been difficult to be water-base, can be made water-base.
- the amount of the vinyl compound used is about 24% based on 100 parts by mass of the combined amount of the vinyl compounds and the condensate (c) containing the epoxy resin and the fatty acid.
- the resulting vinyl-modified epoxy ester resin was a viscous solution containing 80% of non-volatile matter.
- the acid value of the solid content in the solution was 30 mgKOH/g.
- aqueous dispersion of the resulting vinyl-modified epoxy ester resin was an aqueous dispersion having a solid content concentration of 35% and a pH of 9.2.
- LUMINUS manufactured by Maruo Calcium Co., Ltd.
- LUMINUS manufactured by Maruo Calcium Co., Ltd.
- titanium oxide as a pigment
- BYK-028 manufactured by BYK Japan KK
- DICNATE 3111 manufactured by Dainippon Ink & Chemicals, Inc.
- SN thickener 636 manufactured by Sannopuko, Inc.
- Water-base coating compositions were prepared in the same manner as in Example 1, except for changing the recipe given in Table 1.
- Example 4 0.2 part of the above-mentioned silicone-modified epoxy resin was further added to an aqueous dispersion.
- Calcium carbonate A is LUMINUS (manufactured by Maruo Calcium Co., Ltd.)
- calcium carbonate B is SUPER 1700 (manufactured by Maruo Calcium Co., Ltd.).
- Calcium carbonate B which is a product without treatment, does not satisfy the requirements of the calcium carbonate of the present invention.
- Each of coating films of the water-base coating compositions obtained in Example 1 to 5 and Comparative Examples 1 to 3 was checked for its gloss.
- Each of the water-base coating compositions was applied with an applicator and dried in two ways, namely, at 20°C, 50% relative humidity for 1 day and at 20°C, 90% relative humidity for 1 day.
- the applicator was selected so that the film thickness of a dry coating film might become 80 ⁇ 5 ⁇ m.
- the 60° specular glossiness of the resulting coating films were measured.
- Example 1 to 5 In order to evaluate the coating film appearance of the water-base coating compositions obtained in Example 1 to 5 and Comparative Examples 1 to 3, sagging property was examined. Using a sag tester, the water-base coating composition was applied onto a panel made of a glass sheet and the specimen was immediately caused to stand vertically. Whether sagging of a coating occurs or not depending on the thickness of the sample layer was examined.
- the sag tester had six gaps, namely, 20, 25, 30, 35, 40 and 45mil.
- Example 1 to 5 Each of the water-base coating compositions obtained in Example 1 to 5 and Comparative Examples 1 to 3 were applied on an undercoating and then the adhesiveness was examined.
- An oil-base rust preventive coating CR MARINE WHITE PRIMER M (manufactured by Nippon Paint Marine Coatings Co., Ltd.) was spray coated to a 7 cm ⁇ 15 cm steel plate (shot blast steel plate) and then dried at 20°C for 7 days.
- the thickness of the undercoating was 40 ⁇ 5 ⁇ m and the thickness of the top coating was 80 ⁇ 5 ⁇ m.
- This test plate was exposed to a neutral salt spray test machine of JIS K5600-7-1 for 200 hours.
- Table 1 clearly shows that the water-base coating composition by the present invention has been improved in gloss, coating film appearance, anticorrosion property and moisture resistance.
- the water-base coating composition containing a calcium carbonate filler and a vinyl-modified epoxy ester resin having a specific resin composition has excellent gloss, coating film appearance, anticorrosion property and moisture resistance.
- the water-base coating composition of the present invention can be used suitably for coating in the fields of ships and bridges where high anticorrosion property and appearance are required.
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WO2011064323A1 (de) * | 2009-11-27 | 2011-06-03 | Basf Se | Verfahren zur herstellung von polymerhaltigen beschichtungen |
CN104017465A (zh) * | 2014-06-24 | 2014-09-03 | 山东固耐特新材料有限公司 | 一种用于车辆板簧及底盘的水性防腐底漆 |
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KR102388250B1 (ko) * | 2017-06-02 | 2022-04-20 | 주식회사 케이씨씨 | 도료 조성물 및 이를 적용한 천장재 |
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JP7357251B2 (ja) * | 2019-02-04 | 2023-10-06 | 株式会社イーエスティージャパン | 錆抑制塗料及びその製造方法 |
JP2021001314A (ja) * | 2019-06-18 | 2021-01-07 | ベック株式会社 | 水性被覆材 |
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JPS62212480A (ja) | 1986-03-14 | 1987-09-18 | Maruo Calcium Kk | 水系塗料用填剤 |
JP3635127B2 (ja) * | 1994-07-08 | 2005-04-06 | 日本ペイント株式会社 | ブロックポリマーおよびその製造方法、表面改質剤、コーティング材組成物、多層塗膜並びに多層塗膜の形成方法 |
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JPH1036711A (ja) * | 1996-07-22 | 1998-02-10 | Hitachi Chem Co Ltd | 水中硬化塗料用組成物 |
JP3656971B2 (ja) | 1996-12-29 | 2005-06-08 | 日本ペイント株式会社 | ブロックポリマーおよびその製造方法 |
JP4096345B2 (ja) * | 1998-03-20 | 2008-06-04 | 荒川化学工業株式会社 | ビニル変性エポキシエステルおよび水性被覆剤 |
JP2001240792A (ja) * | 2000-02-29 | 2001-09-04 | Nippon Paint Co Ltd | 水性塗料組成物、汚染防止方法および塗装物 |
JP2001294622A (ja) * | 2000-04-10 | 2001-10-23 | Mitsubishi Rayon Co Ltd | 熱硬化性粉体塗料用樹脂及びこれを用いた熱硬化性粉体塗料組成物 |
JP2002188046A (ja) * | 2000-12-21 | 2002-07-05 | Shinto Paint Co Ltd | 防錆力に優れた水性被覆用組成物 |
JP2002233819A (ja) * | 2001-02-08 | 2002-08-20 | Nippon Paint Co Ltd | 鋼材の粉体塗装方法および粉体塗装鋼材 |
JP2003119245A (ja) * | 2001-10-05 | 2003-04-23 | Dainippon Ink & Chem Inc | ビニル変性エポキシエステル樹脂の水分散体、水性塗料組成物および塗装物 |
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2008
- 2008-02-29 NO NO20081085A patent/NO340248B1/no unknown
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Non-Patent Citations (4)
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DATABASE WPI Week 200238 Thomson Scientific, London, GB; AN 2002-343293 XP002519724 & JP 2001 294622 A (MITSUBISHI RAYON CO LTD) 23 October 2001 (2001-10-23) * |
DATABASE WPI Week 200307 Thomson Scientific, London, GB; AN 2003-069972 XP002519725 & JP 2002 233819 A (NIPPON PAINT CO LTD) 20 August 2002 (2002-08-20) * |
DATABASE WPI Week 200413 Thomson Scientific, London, GB; AN 2004-125551 XP002519726 & JP 2003 119245 A (DAINIPPON INK & CHEM INC) 23 April 2003 (2003-04-23) * |
See also references of WO2007015294A1 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011064323A1 (de) * | 2009-11-27 | 2011-06-03 | Basf Se | Verfahren zur herstellung von polymerhaltigen beschichtungen |
CN102630245A (zh) * | 2009-11-27 | 2012-08-08 | 巴斯夫欧洲公司 | 生产含聚合物涂层的方法 |
CN102630245B (zh) * | 2009-11-27 | 2014-10-08 | 巴斯夫欧洲公司 | 生产含聚合物涂层的方法 |
US9011979B2 (en) | 2009-11-27 | 2015-04-21 | Basf Se | Process for producing polymer-containing coatings |
CN104017465A (zh) * | 2014-06-24 | 2014-09-03 | 山东固耐特新材料有限公司 | 一种用于车辆板簧及底盘的水性防腐底漆 |
Also Published As
Publication number | Publication date |
---|---|
KR20080041666A (ko) | 2008-05-13 |
CN101278018B (zh) | 2011-02-16 |
CN101278018A (zh) | 2008-10-01 |
JPWO2007015294A1 (ja) | 2009-02-19 |
EP1916282A4 (de) | 2009-04-22 |
WO2007015294A1 (ja) | 2007-02-08 |
KR100967331B1 (ko) | 2010-07-05 |
EP1916282B1 (de) | 2011-06-29 |
NO340248B1 (no) | 2017-03-27 |
JP4540711B2 (ja) | 2010-09-08 |
NO20081085L (no) | 2008-02-29 |
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